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1.
Heteronuclear Metal Atom Clusters of the Types X4?n[SnM(CO)4P(C6H5)3]n and M2(CO)8[μ-Sn(X)M(CO)4P(C6H5)3]2 by Reaction of SnX2 with M2(CO)8[P(C6H5)3]2 (X = Halogene; M = Mn, Re; n = 2, 3) The compounds of the both types X4?n[SnM(CO)4P(C6H5)3]n (n = 3; M = Mn; X = F, Cl, Br, I. n = 2: M = Mn, Re; X = Cl, Br, I) and M2(CO)8[μ-Sn(X)M(CO)4P(C6H5)3]2 (M = Mn; X = Cl, I. M = Re; X = Cl, Br, I) are prepared by reaction of SnX2 with M2(CO)8[P(C6H5)3]2 (M = Mn, Re). Their IR frequencies are assigned. In Re2(CO)8[μ-Sn(Cl)Re(CO)4P(C6H5)3]2 the central molecule fragment contains a planar Re2Sn2 rhombus with a transannular Re? Re bond of 316.0(2) pm. Each of the SnIV atoms is connected with the terminal ligands Cl and Re(CO)4P(C6H5)3. These ligands are in transposition with respect to the Re2Sn2 ring. The mean values for the remaining bond distances (pm) are: Sn? Re = 274.0(3); Sn? Cl = 243(1), Re? C = 176(5), Re? P = 242.4(9), C? O = 123(5). The factors with an influence on the geometrical shape of such M2Sn2 rings (M = transition metal) are discussed.  相似文献   

2.
Trigonal Bipyramidic Heteronuclear Metal Atom Clusters of the Type closo-Fe3(CO)9-[μ3- MRe(CO)5]2 (M = Ge, Sn) The diamagnetic title compounds were prepared by the reaction of SnCl2 (or Ge/GeCl4), MnRe(CO)10, and Fe(CO)5 at 220°C in a glass tube. The result of the single crystal X-ray analysis of Fe3(CO)93-SnRe(CO)5]2 showed that the triangular molecular fragment of Fe3(CO)9 with a fac-CO ligand arrangement at each Fe atom was capped by two μ3-SnRe(CO)5 groups forming a trigonal bipyramidic metal atom polyhedron. The characterization of its Sn? Re bond length [av. 272,6(2) pm] was undertaken by comparison with that of Cl2Sn[Re(CO)5]2 [277.9(4) pm] obtained from a further structural determination. This type of polyhedron with GeIV and transition metal atoms bonds was before unknown. The ν(CO) i.r. absorption bands of both heteronuclear metal atom clusters and their electron absorption bands above λ = 350 nm were measured.  相似文献   

3.
Perfluoromethyl-Element-Ligands. XVIII. Preparation and Spectroscopic Investigation of M(CO)5L and M(CO)4L2 Complexes [L = MenP(CF3)3?n; n = 0–3; M = Cr, Mo, W] M(CO)5L and cis-M(CO)4L2 complexes, respectively [M = Cr, Mo, W; L = MenP(CF3)3?n; n = 0–3] are prepared reacting M(CO)5 · THF or M(CO)4norbor with L at room temperature. The cis-compounds isomerize above 50°C yielding the trans-complexes; the rate of isomerization increases with increasing number of CF3 groups. Thermal reaction of M(CO)6 (M = Cr, Mo, W) with P(CF3)3 yields M(CO)5P(CF3)3 and trans-M(CO)4[P(CF3)3]2. Introduction of three P(CF3)3 ligands by reaction with M(CO)3(cycloheptatriene) (M = Cr, Mo) proves unsuccessful; besides little M(CO)5P(CF3)3 trans-M(CO)4[P(CF3)3]2 is formed. The new compounds are characterized by analytical and spectroscopic (n.m.r., i.r., MS) methods.  相似文献   

4.
Five new complexes, [M(CO)5(apmsh)] [M = Cr; (1), Mo; (2), W; (3)], [Re(CO)4Br(apmsh)] (4) and [Mn(CO)3(apmsh)] (5) have been synthesized by the photochemical reaction of metal carbonyls [M(CO)6] (M = Cr, Mo and W), [Re(CO)5Br], and [Mn(CO)3Cp] with 2-hydroxyacetophenone methanesulfonylhydrazone (apmsh). The complexes have been characterized by elemental analysis, mass spectrometry, f.t.-i.r. and 1H spectroscopy. Spectroscopic studies show that apmsh behaves as a monodentate ligand coordinating via the imine N donor atom in [M(CO)5(apmsh)] (1–4) and as a tridentate ligand in (5).  相似文献   

5.
The room‐temperature reaction of [Cp*TaCl4] with LiBH4?THF followed by addition of S2CPPh3 results in pentahydridodiborate species [(Cp*Ta)2(μ,η22‐B2H5)(μ‐H)(κ2,μ‐S2CH2)2] ( 1 ), a classical [B2H5]? ion stabilized by the binuclear tantalum template. Theoretical studies and bonding analysis established that the unusual stability of [B2H5]? in 1 is mainly due to the stabilization of sp2‐B center by electron donation from tantalum. Reactions to replace the hydrogens attached to the diborane moiety in 1 with a 2 e {M(CO)4} fragment (M=Mo or W) resulted in simple adducts, [{(Cp*Ta)(CH2S2)}2(B2H5)(H){M(CO)3}] ( 6 : M=Mo and 7 : M=W), that retained the diborane(5) unit.  相似文献   

6.
Phosphido- and Arsenido-bridged Dinuclear Complexes. Synthesis and Molecular Structure of (η5-C5H4R)2Zr{μ-P(SiMe3)2}2M(CO)4 (R = Me, M = Cr; R = H, M = Mo) and Synthesis of (η5-C5H5)2Zr{μ-As(SiMe3)2}2Cr(CO)4 The reaction of (η5-C5H4R)2Zr{E(SiMe3)2}2 with M(CO)4(NBD) (NBD = norbornadiene) yields the dinuclear phosphido- or arsenido-bridged complexes (η5-C5H4R)2Zr{μ-E(SiMe3)2}2M(CO)4 (R = Me, E = P, M = Cr ( 1 ); R = H, E = P, M = Mo ( 2 ); R = H, E = As, M = Cr ( 3 )). No formation of dinuclear complexes was observed in the reaction of (η5-C5H4Me)2Zr{P(SiMe3)2}2 with Ni(PEt3)4, Ni(CO)2(PPh3)2 or with NiCl2(PPh3)2 in the presence of Mg. Complexes 1 – 3 were characterised spectroscopically (i. r., n. m. r., m. s.), and X-ray structure investigations were carried out on 1 and 2 . The central four-membered ZrP2M ring is slightly puckered (dihedral angle between planes ZrP2/CrP2 14.7°, ZrP2/MoP2 14.2°). The Zr? P bond lengths are equivalent ( 1 : Zr? P1 2.654(4), Zr? P2 2.657(4) Å; 2 : Zr? P1 2.6711(9), Zr? P2 2.6585(7) Å), as are the M? P bond lengths (M = Cr ( 1 ): Cr? P1 2.513(4), Cr? P2 2.502(4) Å; M = Mo ( 2 ): Mo? P1 2.6263(7), Mo? P2 2.6311(10) Å). The long Zr ··· M distances of 3.414 Å (M = Cr ( 1 )) and 3.461 Å (M = Mo ( 2 )) indicate the absence of a metal-metal bond.  相似文献   

7.
B3N3Me6Cr(CO)3 reacts with [AsPh4] [SnCl3] and [AsPh4] [GeCl3] in tetrahydrofuran to give [AsPh4]3[Cr(CO)3(SnCl3)3] and [AsPh4]3[Cr(CO)3(GeCl3)3], respectively. According to IR. and 13C-NMR.-data, the tricarbonylate anions possess a meridional configuration. The donor-acceptor properties of SnCl3? and GeCl3? in the anions [Cr(CO)3(ECl3)3]3? (E = Sn, Ge) are very similar. A similar synthesis of [AsPh4]3[Cr(CO)3(SnF3)3] was not successful.  相似文献   

8.
Heterobimetallic Phosphanido-bridged Dinuclear Complexes - Syntheses of cis-rac-[(η-C5H4R)2Zr{μ-PH(2,4,6-iPr3C6H2)}2M(CO)4] (R?Me, M?Cr, Mo; R?H, M?Mo) The zirconocene bisphosphanido complexes [(η-C5H4R)2Zr{PH(2,4,6-iPr3C6H2)}2] (R?Me, H) react with [(NBD)M(CO)4] (NBD?norbornadiene, M?Cr, Mo) to give only one diastereomer of the phosphanido-bridged heterobimetallic dinuclear complexes cis-rac-[(η-C5H4R)2Zr{μ-PH(2,4,6-iPr3C6H2)}2M(CO)4] [R?Me, M?Cr ( 1 ), Mo ( 2 ); R?H, M?Mo ( 3 )]. However, no reaction was observed between [(η-C5H5)2Zr{PH(2,4,6-tBu3 C6H2)}2] and [Pt(PPh3)4]. 1—3 were characterised spectroscopically. For 1—3 , the presence of the racemic isomer was shown by NMR spectroscopy. No reaction was observed at room temperature for 3 and CS2, (NO)BF4, Me3NO or PH(2,4,6-Me3C6H2)2. With Et2AlH or PhC?CH decomposition of 3 was observed.  相似文献   

9.
Syntheses and Crystal Structures of [μ‐(Me3SiCH2Sb)5–Sb1,Sb3–{W(CO)5}2] and [{(Me3Si)2CHSb}3Fe(CO)4] – Two Cyclic Complexes with Antimony Ligands cyclo‐(Me3SiCH2Sb)5 reacts with [(THF)W(CO)5] (THF = tetrahydrofuran) to form cyclo‐[μ‐(Me3SiCH2Sb)5–Sb1,Sb3–{W(CO)5}2] ( 1 ). The heterocycle cyclo‐ [{(Me3Si)2CHSb}3Fe(CO)4] ( 2 ) is formed by an insertion reaction of cyclo‐[(Me3Si)2CHSb]3 and [Fe2(CO)9]. The crystal structures of 1 and 2 are reported.  相似文献   

10.
Octahedral clusters from p-block elements are rare ; however, the only known molecular aggregate of this kind, [{(CO)5Cr}6Sn6]2−, has now been supplemented by the isoelectronic cluster [{(CO)5Cr}6Ge6]2− ( 1 ).  相似文献   

11.
Syntheses, Structure and Reactivity of η3‐1,2‐Diphosphaallyl Complexes and [{(η5‐C5H5)(CO)2W–Co(CO)3}{μ‐AsCH(SiMe3)2}(μ‐CO)] Reaction of ClP=C(SiMe2iPr)2 ( 3 ) with Na[Mo(CO)35‐C5H5)] afforded the phosphavinylidene complex [(η5‐C5H5)(CO)2Mo=P=C(SiMe2iPr)2] ( 4 ) which in situ was converted into the η1‐1,2‐diphosphaallyl complex [η5‐(C5H5)(CO)2Mo{η3tBuPPC(SiMe2iPr)2] ( 6 ) by treatment with the phosphaalkene tBuP=C(NMe2)2. The chloroarsanyl complexes [(η5‐C5H5)(CO)3M–As(Cl)CH(SiMe3)2] [where M = Mo ( 9 ); M = W ( 10 )] resulted from the reaction of Na[M(CO)35‐C5H5)] (M = Mo, W) with Cl2AsCH(SiMe3)2. The tungsten derivative 10 and Na[Co(CO)4] underwent reaction to give the dinuclear μ‐arsinidene complex [(η5‐C5H5)(CO)2W–Co(CO)3{μ‐AsCH(SiMe3)2}(μ‐CO)] ( 11 ). Treatment of [(η5‐C5H5)(CO)2Mo{η3tBuPPC(SiMe3)2}] ( 1 ) with an equimolar amount of ethereal HBF4 gave rise to a 85/15 mixture of the saline complexes [(η5‐C5H5)(CO)2Mo{η2tBu(H)P–P(F)CH(SiMe3)2}]BF4 ( 18 ) and [Cp(CO)2Mo{F2PCH(SiMe3)2}(tBuPH2)]BF4 ( 19 ) by HF‐addition to the PC bond of the η3‐diphosphaallyl ligand and subsequent protonation ( 18 ) and/or scission of the PP bond by the acid ( 19 ). Consistently 19 was the sole product when 1 was allowed to react with an excess of ethereal HBF4. The products 6 , 9 , 10 , 11 , 18 and 19 were characterized by means of spectroscopy (IR, 1H‐, 13C{1H}‐, 31P{1H}‐NMR, MS). Moreover, the molecular structures of 6 , 11 and 18 were determined by X‐ray diffraction analysis.  相似文献   

12.
Metal Complexes with Anionic Ligands of the Main Group IV Elements. IX. Reactions of Trichlorostannide and Trichlorogermide Ions with Complexes of Transition Metals in Low Oxidation States Carhonyl trichlorostannido- and carbonyl trichlorogermido-metalate complexes have been synthesized both by photochemical and thermical substitution reactions of [ECl3]? ions (E = Sn, Ge) with M(CO)6, (M = Cr, Mo, W), Fe(CO)5 Fe3(CO)12, Co2(CO)8, as well as with the metalcarbonyl derivatives (π-arene)M(CO)3, (M = Cr, Mo), (h5-C5,H5,)V(CO)4, Mn(CO)5,Cl, Co(NO)(CO)3, and Fe(NO)2,(CO)2. Mainly the bonding properties of the [ECl3]? ligands are discussed by means of i.r. spectroscopic investigations. The progress of the reactions and the necessary reaction conditions show that the nucleophilic properties oft both anions [ECl3]? are unexpectedly small. The slightly weaker hasicity of [SnCl3]? compared with [GeC13]? arreared, when both anions were reacted with Co2,(CO)8, forming the substitution product. [Co2,(CO)7,SnCl3]? and the products of a “base reaction” Cl3GcCo(CO)4, and [Co(CO)4]?.  相似文献   

13.
New complexes {M(CO)4[Ph2P(S)P(S)Ph2]} (M = Cr, Mo and W), (1a)–(3a), [(1a), M = Cr; (2a), M = Mo; (3a), M = W] and {M2(CO)10[-Ph2P(S)P(S)Ph2]} (M = Cr, Mo, W), [(1b)–(3b) [(1b), M = Cr; (2b), M = Mo; (3b), M = W]] have been prepared by the photochemical reaction of M(CO)6 with Ph2P(S)P(S)Ph2 and characterized by elemental analyses, f.t.-i.r. and 31P-(1H)-n.m.r. spectroscopy and by FAB-mass spectrometry. The spectra suggest cis-chelate bidentate coordination of the ligand in {M(CO)4[Ph2P(S)P(S)Ph2]} and cis-bridging bidentate coordination of the ligand between two metals in (M = Cr, Mo and W).  相似文献   

14.
The reaction of [(Cp*Mo)2(μ‐Cl)2B2H6] ( 1 ) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO)2}2{μ‐η22‐B2H4}] ( 2 ). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged Cs structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum–alkyne complex [{CpMo(CO)2}2C2H2]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO)4] fragment, [{Cp*Mo(CO)2}2 B2H2W(CO)4] ( 3 ) was isolated upon treatment with [W(CO)5?thf]. Compound 3 shows the intriguing presence of [B2H2] with a short B?B length of 1.624(4) Å. We isolated the tungsten analogues of 3 , [{Cp*W(CO)2}2B2H2W(CO)4] ( 4 ) and [{Cp*W(CO)2}2B2H2Mo(CO)4] ( 5 ), which provided direct proof of the existence of the tungsten analogue of 2 .  相似文献   

15.
Addition of Cationic Lewis Acids [M′Ln]+ (M′Ln = Fe(CO)2Cp, Fe(CO)(PPh3)Cp, Ru(PPh3)2Cp, Re(CO)5, Pt(PPh3)2, W(CO)3Cp to the Anionic Thiocarbonyl Complexes [HB(pz)3(OC)2M(CS)] (M = Mo, W; pz = 3,5‐dimethylpyrazol‐1‐yl) Adducts from Organometallic Lewis Acids [Fe(CO)2Cp]+, [Fe(CO)(PPh3)Cp]+, [Ru(PPh3)2Cp]+, [Re(CO)5]+, [ Pt(PPh3)2]+, [W(CO)3Cp]+ and the anionic thiocarbonyl complexes [HB(pz)3(OC)2M(CS)] (M = Mo, W) have been prepared. Their spectroscopic data indicate that the addition of the cations occurs at the sulphur atom to give end‐to‐end thiocarbonyl bridged complexes [HB(pz)3(OC)2MCSM′Ln].  相似文献   

16.
Synthesis, Structure, and Reactivity of the Ferrioarsaalkene [(η5‐C5Me5)(CO)2FeAs=C(Ph)NMe2] Reaction of equimolar amounts of the carbenium iodide [Me2N(Ph)CSMe]I and LiAs(SiMe3)2 · 1.5 THF afforded the thermolabile arsaalkene Me3SiAs = C(Ph)NMe2 ( 1 ), which in situ was converted into the black crystalline ferrioarsaalkene [(η5‐C5Me5)(CO)2FeAs=C(Ph)NMe2)] ( 2 ) by treatment with [(η5‐C5Me5)(CO)2FeCl]. Compound 2 was protonated by ethereal HBF4 to yield [(η5‐C5Me5)(CO)2FeAs(H)C(Ph)NMe2]BF4 ( 3 ) and methylated by CF3SO3Me to give [(η5‐C5Me5)(CO)2FeAs(Me)C(Ph)NMe2]‐ SO3CF3 ( 4 ). [(η5‐C5Me5)(CO)2FeAs[M(CO)n]C(Ph)NMe2] ( 5 : [M(CO)n] = [Fe(CO)4]; 6 : [Cr(CO)5]) were isolated from the reaction of 2 with [Fe2(CO)9] or [{(Z)‐cyclooctene}Cr(CO)5], respectively. Compounds 2 – 6 were characterized by means of elemental analyses and spectroscopy (IR, 1H, 13C{1H}‐NMR). The molecular structure of 2 was determined by X‐ray diffraction analysis.  相似文献   

17.
Preparation, Properties, and Molecular Structures of a Rigid Tridentate Chelate Ligand N, N′-Bis(diphenylphosphino)-2, 6-diaminopyridine with MII and M0 Transition Metals [MII = Ni, Pd, Pt; M0 = Cr, Mo, W] The reaction of chlorophenylphosphane and 2, 6-Diaminopyridine give N, N′-Bis-(diphenylphosphino)-2, 6-diaminopyridine (PNP). Two types of complexes [M(PNP)Cl]Cl · L (M = Ni, L = H2O; M = Pd, L = C2H5OH; M = Pt) and mer-[M(PNP)(CO)3] · 2 THF (M = Cr, Mo, W) have been prepared using PNP. These coordination compounds have been characterized by means of i.r., u.v., 31P and 1H n.m.r. measurements. The determination of the molecular structure of the two triclinic substances mer-[Mo(PNP)(CO)3] · 2 THF and [Ni(PNP)Cl]Cl · H2O show that the octahedral Mo(d6) and the square planar nickel (d8) compounds contain a nearly planar tridentate chelate ring system (two fused five-membered rings of the type ) in which the observed bond distances are in accordance with a π electron delocalization effect. The observed gram susceptibility of the diamagnetic Ni(d8) compound remains unchanged between 293 and 410 K. The relative activation property for a homogenous catalytic standard hydrogenation reaction of styrene to ethylbenzene decreases in series of catalysts of type [M(PNP)Cl]Cl · L with MII = Ni > Pd > Pt.  相似文献   

18.
The structure of the title hybrid salt, (C5H8NS)[SnCl3], is built up from segregated layers of organic cations and Sn polyhedra. [SnCl3]? groups are linked together by weak Sn?Cl interactions to form a one‐dimensional polymeric chain of anions.  相似文献   

19.
Perfluoromethyl Element Ligands. XXXII. Reactions of the Metal Hydrides π-C5H5(CO)3MH (M = Cr, Mo, W) with Diphosphanes [Ph2?nYnP]2 (Y = I, CN, SiMe3; n = 2, 1, 0) The reactions of π-C5H5(CO)3MH (M = Cr, Mo, W) ( 1a – c ) with the symmetric diphosphanes (Ph2P)2, [Ph(CN)P]2, [(CN)2P]2, and the cyclophosphane (PPh)5, respectively, occur under cleavage of the P? P bond. The reactivity decreases in the series The tendency to form binuclear complexes reflects the basicity of the metallated phosphanes π-C5H5(CO)3MPRR′ and increases in the order P(CN)2 < P(CN)Ph ? P(Ph)H < PPh2. Iodine containing diphosphanes [Ph(I)P? P(I)Ph and P2I4] undergo redox reactions with 1a – c , yielding π-C5H5(CO)3MI and unstable iodo-diphosphanes. No P? P bond cleavage occurs in the reaction of the silyl substituted diphosphanes [Ph(SiMe3)P]2 and [(Me3Si)2P]2 with 1a – c , but P? Si bond fission is the preferred reaction giving π-C5H5(CO)3MSiMe3.  相似文献   

20.
Metal Complexes with Anionic Ligands of Elements of the Main Group IV. VIII Pentacarbonyltrihalogenostannidometalate(O) Complexes of Chromium, Molybdenum, and Tungsten with Fluorine and Iodine Containing Trihalogenostannido Ligands In methylenechloride [As(C6H5)4][SnF3] readily reacts with the metalhexacarbonyls forming the arsoniumsalts of the pentacarbonyltrifluorostannidometalate(O) complexes, [M(CO)5SnF3]? (M ? Cr, Mo, W). Exclusively by the reaction of the intermediately formed complex Cr(CO)5THF only one pure triiodostannidometalate(O) Complex, [N(C2H5)4][Cr(CO)5SnJ3], could be isolated. The trihalogenostannidometalate(O) complexes [M(CO)5SnClX2]? (X ? F: M ? Cr, Mo, W; X ? J: M ? Cr) could be prepared by SnX2-insertion reactions of the [M(CO)5Cl]? complexes. The bonding properties of the halogenostannide ions are discussed on the bases of the IR spectra of their metalate(O) complexes.  相似文献   

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